|Publication number||US3904557 A|
|Publication date||Sep 9, 1975|
|Filing date||Feb 26, 1974|
|Priority date||Oct 26, 1972|
|Publication number||US 3904557 A, US 3904557A, US-A-3904557, US3904557 A, US3904557A|
|Inventors||James Leverette Guthrie, Lenore J Huffman|
|Original Assignee||Grace W R & Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (4), Referenced by (17), Classifications (16), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
UNITED STATES PATENTS 5/1961 Anderson 260/2.5 AK
United States Patent [1 1 [111 3,904,557 Guthrie et a1. Sept. 9, 1975  METHOD FOR PRODUCTION 'OF A 3,137,671 6/1964 Bosshard 260/25 AK MULTICOLORED URETHANE SPONGE 3,239,474 3/1966 Cwik 260/25 AK 3,278,486 10/1966 Meek 260/25 AK  Inventors: James Leverette Guthrie, Ashton;
Lenore J. Huffman, Ellicott City, OTHER PUBLICATIONS both of Given, Modern Encyclopedia of Cooking, Vol. 1, J. G.  Assignee: R. Grace & C0. New York Ferguson & Assoc, Chicago, 1949, pp. 580-581.
N.Y. Marsh, The Good Housekeeping Cook Book, Rinehart Filed: Feb. 1974 & Co., N.Y. 1949, pp. 663 and 672. I
Technical Data Bulletin D-24, Coloring Polyether PP 446,043 Urethane Flexible Foam, Allied Chemical Corp.,
Related us. Application Data 1962 W 1 6 S.N.30939 .6 3] fgg g ggs ag of er 0 0 Oct 2 Primary Examiner-Melvyn I. Marquis Assistant ExaminerC. Warren Ivy 52 us, (:1, .;.'260/2.s BD; 260/2.5 AK; Attorney, Agent, or FirmEugene M. Bond 260/DIG. 26; 264/73; 264/77  Int. Cl.....C08g 22/48; C08g 51/14; C08g 51/66 57 ABS R CT  Field of Search""260/2'5 BD; The invention disclosed is for a. method of preparing a new multicolored variegated sponge wherein several  References Cited colors are heterogeneously associated in a given article.
1 Claim, N0 Drawings METHOD FOR PRODUCTION OF A MULTICOLORED URETHANE SPONGE This application is a continuation-in-part of application Ser. No. 300,939, filed Oct. 26, 1972, now abandoned.
This invention relates to a new multicolored variegated sponge. More particularly, the invention relates to a method of producing a multicolored variegated sponge wherein the several colors are heterogeneously associated in the color combinations employed.
Sponges are available to the art wherein a single uniform color is disposed alone or with a printed design thereon. Because of difficulties associated with preparation of sponges from materials such as polyurethanes, multicolored variegated sponges have not been available to the art. It has now been found, however, that by practice of the present invention there is provided new multicolored variegated sponges wherein the several colors are heterogeneously associated in a given article.
It has now been found that a unique multicolored variegated sponge comprising a heterogeneous multicolored foam may be obtained in accordance with the present invention by heterogeneously associating a plurality of differently colored masses prior to foaming. This invention arises out of the surprising discovery that the incorporation of color additions in base formulations prior to foaming enables the production of the heterogeneous color associations by the practice of this invention.
Thus, the present invention provides a multicolored foam product wherein the colors are so combined that a heterogeneous color effect is'produced with the separate colors being sharply delineated.
The present invention also provides a method for preparing such multicolored foams wherein the multicolors are combined in distinctive fashion in an initial bun which is severed into multiple units of individual foam products of desired configuration all having a heterogeneous association of colors.
More particularly, the invention provides a method for the preparation of multicolored foam products hav ing at least two distinctively different shades of base formulation which comprises preparing a base formulation, adding distinctively different coloring agents to separate portions of the base formulation, foaming the separate base formulations while combining the colored base formulations into a unitary product having substantially complete color separation. The unitary product may be then sectioned into individual sponges of desired shape and size.
in the present method, a base formulation is prepared from a mixture of ingredients preferably free of coloring pigments and which are blended in a tank. If desired, different base formulations may be prepared for each separate coloring agent to be utilized in the final product or, a single base formulation may be prepared which is divided and subsequently combined with desired colors and pigments. Regardless of how the base formulations are prepared, it is desirable that the base formulations for each color have substantially similar consistencies to produce a uniform product when combined.
After the base formulations have been prepared, individual portions are taken and received in color blend ing tanks. At least two distinctively different colors are then added to separate portions of the base formulation in the color blending tanks and dispersed by stirrers. In this manner, a plurality of distinctively colored base compositions are prepared for further processing. The base formulations, the coloring agents, and any additive agents may all be combined by any of the mixing methods well known to the art. Also, additional colors and coloring tanks may be used to prepare and combine colored bases as described to give a multicolored product in which more than two distinct colors are combined.
After the colors and pigments have been added to and combined with the base formulation in color blending tanks, and uniformly blended, the formulation is ready for foaming reaction.
The color additives may be introduced either by way of the resin base formulation as previously indicated or otherwise may be introduced by reactant materials used for foaming. It is important that the color additives be soluble or dispersable in either the resin or base formulation, or in materials to be reacted therewith. For example, where an aqueous reactant is employed to effect foaming of the base formulation, the color additive is first blended with the aqueous reactant prior to reaction.
The blended color-containing formulations from the color blending tanks with all reactants for foaming are allowed to flow to a heterogeneous blender. Thus, foaming reaction is initiated prior to combining the color formulations at the heterogeneous blender.
The heterogeneous blender may comprise most any suitable means', including simple hand paddle mixing, which is insufficient to homogenize the colors. Thus, this blender may be most any means which lightly mixes the foaming compositions under laminar-flow conditions. It is recognized that the greater the degree of blending at this location, the greater will be the blending resulting in less contrast of large sections of multi-color effect in the product. Laminar-flow conditions for color blending may be achieved by maintaining a slight reservoir at the constriction of a funnel shaped heterogeneous blender, i.e., the point where the colors are blended. A more desirable method of achieving laminar-flow blending conditions in the heterogeneous association of colored base formulations is to add a divider plate in the funnel for each particular color. Dividing partitions such as annular, sectional and the like may also be employed to impart various design characteristics to the heterogeneous association of colored base formulations. The funnel may be rotated while the exit flow of blended colors is directed into a suitable mold.
Additional procedures may be devised to create desirable swirl and marbelized design effect which may readily be adapted to the present process such as, for example, by employing rotational motion of spigots in place of the funnel, noncircular motion of the funnel, or of the mold, mold oscillating under a stationary funnel, mold oscillating under a rotating funnel, mold rotating under an oscillating funnel, or the like. Other suitable combinations may also be devised which deliver at least two distinctively different colors into heterogeneous association under laminar-flow conditions. The apparatus should therefore be designed to avoid turbulent flow during the combining of the colors.
The term heterogeneously associated as used herein means the intimate combination of distinctively different colored base compositions to form a mass having virtually complete color separation which may 3 be easily perceived by the unaided, naked eye.
The compositions for use in base formulations include generally materials useful for polyurethane foam generation. Typically, these foams have been based on reaction of a polyisocyanate using reactants which may include materials such as polyoxyethylene polyol, polyisocyanate, and possibly a catalyst or surfactant which are then foamed.
The polyoxyethylene polyol may have a weight average molecular weight of about 200 to about 20,000, and preferably between about 600 to about 6,000, with a hydroxyl functionality of about 2 or greater, preferably from about 2 to about 8.
Polyoxyethylene polyol is terminated or capped by reaction with a polyisocyanate. The reaction may be carried out in an inert moisture-free atmosphere such as under a nitrogen blanket, at atmospheric pressure at a temperature in the range of from about to about 120C. for a period of time of about 20 hours depending upon the temperature and degree of agitation. This reaction may be effected also under atmospheric conditions provided the product is not exposed to excess moisture. The polyisocyanates used for capping the polyoxyethylene polyol include polyisocyanates and ping is between about 1 to about 4 isocyanate to hydroxyl, and preferably about 2 to about 3 isocyanate to hydroxyl molar ratio. In order to achieve an infinite network formation on foaming, the reactive components may be formulated and reacted subsequent to color addition, using polyurethane reactions for foaming well known to the art.
The coloring agents usefully employed in this invention to provide proper coloring to the base formulation prior to their being heterogeneously associated includes those well known to the art such as, for example, Food, Drug and Cosmetic certified colors and inert pigments. These dyes and pigments may be added in an amount from about 5 to about 20 parts by weight for each 100 parts by weight of base. Typical dyes known to the art may include water soluble and water insoluble dyes.
Coloring agents useful herein having a Colour Index Number falling within 10,000 and 77,999.
Dyes and pigments which are useful include those dyes of the types (Colour Index Numbers falling within 10,000 to 77,999) listed in the table (resproduced below as Table I) which occurs on the first page of the Preamble to Part II (in Volume 3) of the Second polyisothiocyanates which are PAPI-l (a polyaryl poly- (1956) Edition of the Colour Index.
TABLE I Classification of Dyes & Pigments C.I. Numbers C.l. Numbers Nitroso l0000- l 0299 Indamine 49400-49699 Nitro l0300-l0999 lndophenol 49700-49999 Monoazo l 1000-19999 Aline 50000-50999 Disazo 20000-29999 Oxazine 51000-5 1999 Trisazo 30000-34999 Thiazine 52000-52999 Polyazo 35000-36999 Sulfur 53000-54999 Azoic 37000-39999 Lactone 55000-55999 Stilbene 40000-40999 'Aminoketone 56000-56999 Diphenylmcthane 4 l 000-4 l 999 Hydroxyketone 5 7000-5 7999 Triarylmethane 42000-44999 Anthraquinone 58000-72999 Xanthene 45000-45999 lndigoid 73000-73999 Acridine 46000-46999 Phthalocyanine 74000-74999 Quinoline 47000-47999 Natural 75000-75999 Methine 48000-48999 Oxidation Bases 76000-76999 Thiazole 49000-49399 Inorganic Pigments 77000-77999 *This table is from the first page of the Preamble To Pan ll of the Second 1956 Edition of the Colour Index.
isocyanate as defined in US. Pat. No. 2,683,730), tolpages 495-589 of volume 15 of the Kirk-Othmer Encyylene diisocyanate, triphenylmethane-4, 4,4,- clopedia of Chemical Technology, second edition triisocyanate, benzene-1,3,5-triisocyanate, toluene- (1968) lists a large number of pigments which can be 2,4,6-triisocyanate, diphenyl-2,4,4'-triisocyanate, hexamethylene diisocyanate, xylene diisocyanate, chlorophenylene diisocyanate, diphenylmethane-4,4'- diisocyanate, naphthalene-l, 5-diisocyanate, xylenealpha,alpha -diisothiocyanate, 3 3 '-dimethyl-4,4 biphenylene diisocyanate, 3,3-dimethoxy-4,4-biphenylene diisocyanate, 2,2,5,5'-tetramethyl-4,4-biphenylene diisocyanate, 4,4-methylenebis(phenylisocyanate) 4,4'-sulfonylbis(phenylisocyanate) 4,4-methylene di-orthotolylisocyanate, ethylene diisocyanate, ethylene diisothiocyanate, trimethylenediisocyanate andthe like. Mixtures of any one or more of the above mentioned organic isothiocyanates or isocyanates may be used as desired. The aromatic diisocyanates and polyisocyanates or mixtures thereof which are especially suitable are those which are readily commercially available, have a high degree of reactivity and a relatively low cost.
Capping of the polyoxyethylene polyol may be effected using stoichiometric amounts of reactants. Desirably, however, an excess of isocyanate is used to insure complete capping of the polyol. Thus, the ratio of isocyanate groups to the hydroxyl groups used for capused in practice of this invention. Among the useful pigments are:
TABLE II red, and synthetic iron oxide pigments (including synthetic oxides) red lead orange mineral cadmium reds cadmium maroons cadmium yellows cuprous oxide cinnabar raw umber metallic browns (mineral browns) manganese brown Van Dyke brown chrome yellows chrome oranges molybdenum oranges zinc yellow nickel titanate chrome greens (Brunswick greens) TABLE III pigment yellow 1 pigment yellow 3 pigment yellow 12 pigment yellow 13 pigment yellow 14 pigment yellow 17 pigment orange 1 pigment orange 5 pigment orange 13 pigment orange 16 pigment red 1 pigment red 2 pigment red 3 pigment red 4 pigment red 5 pigment red 6 pigment red 17 pigment red 18 brown iron pigment red 22 pigment red 23 pigment red 38 pigment red 48 5 pigment red 49 pigment red 52 pigment red 53 pigment red 54 pigment red 5 7 pigment red 60 pigment red 63 pigment red 81 pigment red 83 pigment red 90 acid red 26 pigment violet 1 pigment violet 3 pigment violet 5 pigment blue 1 pigment blue 2 pigment blue 9 pigment blue 14 pigment blue 15 pigment blue 19 pigment blue 24 pigment green 1 pigment green 2 pigment green 4 pigment green 7 pigment green 8 natural black 3 The following materials, recommended for use in urethane foams, are also useful herein.
TABLE IV 1 NAOCOPERM Red Violet 1 NACCOPERM Blue 1 NACCOPERM Yellow R 1 NACCOPERM Orange R 1 NACCOPERM Vermillion 1 NACCOPERM Scarlet 1 NACCOPERM Violet 1 NACCOPERM Blue R 1 NACCOPERM Blue G 1 NACCOPERM Green 1 NACCOPERM Dark Blue 1 NACCOPERM Orange Y 1 NACCOPERM Magenta Benzidene Yellow Aquabllak 41 Aquabllak K Aquablak No. l
Coloidex No. 3
(Allied Chemical Co.) (Columbian Carbon Co.)
The following pigments recommended for use in urethane foams by Frisch and Saunders, High Polymers, Volume XVI, P. 50 (Interscience, 1964) may also be used.
TABLE V Supplier Color Index Red Vulcan Pink G (PR 477) Verona 45150 Permanent Carmine FBB Extra Verona 12490 Permanent Carmine FR Extra (PR 398) General Dyestuff Heliogen Green GA and GB (PR 483) General Dyestuff 7426C Phthalocyanine Green GV (PR 483) Verona 74260 TABLE V-continued Supplier Color Index Resoform Brilliant Green GP General Dyestuff Blue Heliogen Blue CV and BNC (PR 481 Phthalocyanine Blue BF (PR 48 l) Resoform Brilliant Blue B! General Dyestuff Verona General Dyestuff Black Philblack A Pigment Fast Black TW Philips Petroleum Verona EXAMPLE 1 To a reaction vessel containing 3,092 grams, representing 1 mole, 3 eq. CH, of a triol prepared from potassium hydroxide catalyzed reaction of 92 grams anhydrous glycerol with 3300 grams of ethylene oxide, were added 522 grams, representing 3 moles, 6 eq. NCO of tolylene diisocyanate having about 80/20 mixture of 2,4 isomer/2,6 isomer. The reaction exotherm was kept at 70C. by external cooling with water, while stirring for 4 hours. The actual isocyanate content, determined by titration with standard n-butylamine solution in toluene, remained at the constant level of 0.79 meq. NCO/- gram. 0.5 gram of a silicone surfactant, commercially available under the mark L520 by Union Carbide, was added to 200 grams of recovered resin reactant.
0.5 gram of Acridine red dye was dissolved in a first portion of 50 grams of water; 0.5 gram of Naphthol Green B was dissolved in a second portion of 50 grams of water; and 0.5 gram of methyl yellow in a third portion of 50 grams of water. Three 50 gram portions of recovered resin reactant were taken and each separately reacted with each portion of dye containing water. Each mixture was stirred approximately 20 seconds until a uniform creamy stage of foaming was reached. The three batches with different colors were made simultaneously, and these were poured into a cubical mold which was 6 inches on each side. The desired degree of color mixing was done by stirring with a spatula. The foam filled the mold, then gelled within minutes. It was removed from the mold and cut into slices with an electric knife, revealing different tricolored patterns in each slice.
EXAMPLE 2 The procedure of Example 1 was repeated except that the polymer was prepared as follows.
A solution of 92 grams glycerol representing 1 mole, 3 eq. OH, and 134 grams of trimethylolpropane representing 1 mole, 3 eq. OH was outgassed at 100C. and 10 Torr for 2 hours. To the outgassed solution was added 870 grams representing 5 moles tolylene diisocyanate having an /20 mixture of 2,4 isomer/2,6 isomer. The reaction solution was stirred at 60C. for 4 hours whereupon the actual isocyanate content reacted a constant 2.49 meq. NCO/gram relative to a theoretical content of 2.54. The resin product had a pale orange color, a density of 1.10, and a viscosity (Brookfield No. 4 spindle) at 25C. of 13,400 cps. The results of this example were similar to those of Example 1 in preparing the multicolored sponge.
EXAMPLE 3 The procedure of Example 2 was repeated except using polyethylene glycol having a weight average molecular weight of 1,540 in place of trimethylolpropane. Corresponding results were realized except the foam appeared to have slightly smaller cell diameters.
EXAMPLE 4 The procedure of Example 3 was repeated except using polyethylene glycol having a weight average molecular weight of 1800. Corresponding results were realized.
EXAMPLE 5 The procedure of Example 1 was repeated using as one dye, 0.5 gram Calcotone Green G, 0.3 gram Calcotone Blue GPN as a second dye and 0.2 gram Oil Yellow 3G as a third dye. Corresponding results were real ized.
EXAMPLE 6 The procedure of Example 5 was repeated except that the colored resin was foamed in a mold having the shape of a rabbit. The resultant multicolored sponge proved useful as a bath sponge for children.
EXAMPLE 7 The procedure of Example 5 was repeated using combinations of the following dyes:
Plasto Red B (Allied) Plasto Blue RDA (Allied) Oil Yellow 3G (Allied) lndex No. 21120 Calcotone Red B (Cyanamide) lndex No. 2! Calcotone Blue GPN (Cyanamide) Calcotone Violet RP (Cyanamide) Calcotone Green G (Cyanamide) -continued Color Index Calco Oil Orange 207078 (Cyanamide) 10 polymer by capping polyoxyethylene polyol with polyisocyanatc, the polyoxyethylene polyol having a weight average molecular weight of about 200 to about 20,000 and a hydroxyl functionality of about 2 to about 8, adding distinctively different colored compositions easily perceived by the unaided, naked eye to separate portions of the prepolymer or water, said colored compositions being water-soluble or dispersable in water or the prepolymer, mixing the separate colored portions of prepolymer or water with respective portions of water or prepolymer to form separate colored foaming masses, and mixing said foaming masses under laminar flow conditions to form a unitary product having substantially complete color separation, and recovering a multicolored variegated polyurethane foam.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US2986536 *||Dec 7, 1956||May 30, 1961||Allied Chem||Process for coloring polyurethane foams|
|US3137671 *||Mar 16, 1959||Jun 16, 1964||Ciba Ltd||Process for the production of colored polyurethane plastics|
|US3239474 *||Feb 14, 1962||Mar 8, 1966||Glidden Co||Foamed polyurethane having a marbleized appearance and process for making same|
|US3278486 *||Feb 17, 1959||Oct 11, 1966||Scripto Inc||Colored polymeric materials|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4105594 *||May 18, 1976||Aug 8, 1978||Bayer Aktiengesellschaft||Highly filled polyurea foams|
|US4129694 *||Apr 7, 1976||Dec 12, 1978||W. R. Grace & Co.||Fabric softener urethane foam and method|
|US4456707 *||Apr 11, 1983||Jun 26, 1984||Bayer Aktiengesellschaft||Process for the production of fiber-containing polyurethane moldings having inhomogeneously colored surfaces|
|US4638017 *||Dec 9, 1985||Jan 20, 1987||Minnesota Mining And Manufacturing Company||Hydrophilic polyurethane/polyurea sponge|
|US4738992 *||Jun 17, 1986||Apr 19, 1988||Minnesota Mining And Manufacturing Company||Hydrophilic polyurethane/polyurea sponge|
|US4923903 *||Jan 24, 1989||May 8, 1990||Minnesota Mining And Manufacturing Company||Dyed aqueous air foams|
|US5081162 *||Jul 20, 1990||Jan 14, 1992||Woodbridge Foam Corporation||Process for producing foamed polymers|
|US5276064 *||Jun 28, 1993||Jan 4, 1994||Industrial Thermo Polymers Limited||Colored extruded foam cross-linked backer rod|
|US5597485 *||Dec 27, 1994||Jan 28, 1997||Vilmax S.A.||Process for separating proteins|
|US5876597 *||Dec 11, 1996||Mar 2, 1999||Vilmax S.A.||Anionic dye-containing polymer|
|US6767932||Jun 6, 2001||Jul 27, 2004||Wm. T. Burnett & Co.||Method and apparatus for producing discretely striped multi-property foam|
|US20030175526 *||Mar 12, 2002||Sep 18, 2003||Guang-Huo Lin||Shoe sole structure|
|US20050194707 *||Mar 3, 2004||Sep 8, 2005||Jone Chang||Method for manufacturing pliable sponge|
|US20060063861 *||Sep 17, 2004||Mar 23, 2006||Milliken & Company||Method for employing colorants as indicators in polymer blending|
|US20070228597 *||Mar 30, 2006||Oct 4, 2007||Mutton William J||Swirl material|
|WO2006036345A2 *||Aug 16, 2005||Apr 6, 2006||Milliken & Company||Method for employing colorants as indicators in polymer blending|
|WO2006036345A3 *||Aug 16, 2005||Nov 9, 2006||Milliken & Co||Method for employing colorants as indicators in polymer blending|
|U.S. Classification||521/159, 521/99, 264/73, 264/77, 260/DIG.260|
|International Classification||C08J9/00, C08G18/48, B44C5/00|
|Cooperative Classification||C08G18/4833, Y10S260/26, C08J2375/04, B44C5/00, C08J9/0004|
|European Classification||C08J9/00H, C08G18/48F, B44C5/00|
|Mar 22, 1993||AS||Assignment|
Owner name: HAMPSHIRE CHEMICAL CORP., MASSACHUSETTS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:W.R. GRACE & CO.-CONN.;REEL/FRAME:006467/0595
Effective date: 19921229
|Mar 8, 1993||AS||Assignment|
Owner name: CHASE MANHATTAN BANK (NATIONAL ASSOCIATION), AS CO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HAMPSHIRE CHEMICAL CORP.;REEL/FRAME:006621/0379
Effective date: 19921229
|Aug 5, 1988||AS||Assignment|
Owner name: W.R. GRACE & CO.-CONN.
Free format text: MERGER;ASSIGNORS:W.R. GRACE & CO., A CORP. OF CONN. (MERGED INTO);GRACE MERGER CORP., A CORP. OF CONN. (CHANGED TO);REEL/FRAME:004937/0001
Effective date: 19880525